The importance of broccoli (Brassica oleracea var. italica) consumption has increased in recent years due to its significant amount of anticarcinogenic and antioxidant compounds, as well as its many vitamins. However, broccoli florets are a highly perishable product which rapidly senesce and turn yellow after harvest, resulting in losses in nutritional and bioactive compounds. Thus, in this study, we evaluated the effect of postharvest exogenous of salicylic acid (SA) and calcium chloride (CaCl2) and their combination on the quality of broccoli florets stored at 5 °C for 28 days to minimize the rapid senescence of broccoli florets. Samples treated with 2 mM SA alone or in combination with 2% CaCl2 showed lower weight loss and lower losses of chlorophyll content, vitamin C, phenolic compounds, carotenoids, flavonoids, and glucosinolates compared with the control samples. Additionally, antioxidant activity was maintained by either SA or SA + CaCl2 treatments while peroxidase activity was decreased. For higher quality and lower losses in antioxidant compounds of broccoli florets during refrigerated storage at 5 °C, SA + CaCl2 treatment could be helpful for up to 21 days.